Air-Water Interface Effects on the Regioselectivity of Singlet Oxygenations of a Trisubstituted Alkene.
نویسندگان
چکیده
The regioselective synthesis of allylic hydroperoxide sulfonates by singlet oxygenation at the air-water interface has been found to depend on the concentration of the alkene sulfonate and added calcium salt. The regioselectivity is proposed to originate from an orthogonal alkene relative to the water surface for preferential methyl hydrogen abstraction by airborne singlet oxygen in an ene reaction. The findings hint that the air-water interface is a locale for synthetic reactions.
منابع مشابه
"Ene" Reactions of Singlet Oxygen at the Air-Water Interface.
Prenylsurfactants [(CH3)2C═CH(CH2)nSO3(-) Na(+) (n = 4, 6, or 8)] were designed to probe the "ene" reaction mechanism of singlet oxygen at the air-water interface. Increasing the number of carbon atoms in the hydrophobic chain caused an increase in the regioselectivity for a secondary rather than tertiary surfactant hydroperoxide, arguing for an orthogonal alkene on water. The use of water, deu...
متن کاملSynergism between Airborne Singlet Oxygen and a Trisubstituted Olefin Sulfonate for the Inactivation of Bacteria
The reactivity of a trisubstituted alkene surfactant (8-methylnon-7-ene-1 sulfonate, 1) to airborne singlet oxygen in a solution containing E. coli was examined. Surfactant 1 was prepared by a Strecker-type reaction of 9-bromo-2-methylnon-2-ene with sodium sulfite. Submicellar concentrations of 1 were used that reacted with singlet oxygen by an "ene" reaction to yield two hydroperoxides (7-hydr...
متن کاملTurbulent Events and Gas-Side Mass Transfer Coefficients in a Wavy Air-Water Stratified Flow
Turbulence structure on the gas side of a wavy stratified flow was experimentally investigated in a near horizontal 18.7 cm (H) 10 cm (W) 5.5m (L) rectangular duct.By applying the Variable Interval Time Averaging (VITA) technique to the hot wire anemometer measurements frequency of occurrence of turbulent events were detected near the air-water interface. Experimental results showed that fr...
متن کاملThionin-sensitized intrazeolite photooxygenation of trisubstituted alkenes: substituent effects on the regioselectivity as probed through isotopic labeling.
The regioselectivity for the intrazeolite photooxygenation of several trisubstituted alkenes with geminal dimethyl groups was examined. The length of the alkyl chain at the lone position was varied, and as end groups, the phenyl or the cyclohexyl functionalities were chosen. The general trend for all alkenes is a significant increase of the reactivity at the twin position compared to the photoo...
متن کاملThe Nitrilimine-Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices.
Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine-alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine-alkene cycloadditions were analyzed, for which we could f...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Tetrahedron letters
دوره 56 30 شماره
صفحات -
تاریخ انتشار 2015